CN110075826B - Oxygen-containing defect BiSbO4Preparation method and application of photocatalyst - Google Patents
Oxygen-containing defect BiSbO4Preparation method and application of photocatalyst Download PDFInfo
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- CN110075826B CN110075826B CN201910441884.7A CN201910441884A CN110075826B CN 110075826 B CN110075826 B CN 110075826B CN 201910441884 A CN201910441884 A CN 201910441884A CN 110075826 B CN110075826 B CN 110075826B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 84
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 71
- 239000001301 oxygen Substances 0.000 title claims abstract description 71
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 230000007547 defect Effects 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000005286 illumination Methods 0.000 claims abstract description 28
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- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
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- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
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- 238000007146 photocatalysis Methods 0.000 claims description 7
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- 230000035484 reaction time Effects 0.000 claims description 4
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- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/39—
Abstract
The application discloses oxygen defect BiSbO4A preparation method of a photocatalyst and application thereof, wherein the method comprises the following steps: mixing bismuth nitrate pentahydrate and antimony trioxide according to a molar ratio (1.5-2):1, and adding 10ml of deionized water, and magnetically stirring at normal temperature until the mixture is dissolved; then, dropwise adding a sodium hydroxide solution to adjust the pH value to 1; carrying out high-temperature hydrothermal reaction on the solution with the pH adjusted, and cooling to obtain a mixed system; centrifugally washing the precipitate of the mixed system with water and absolute ethyl alcohol and drying the precipitate to obtain pure-phase BiSbO4(ii) a Pure phase BiSbO obtained in the above step4Carrying out ultraviolet illumination reaction to obtain the oxygen-containing defect BiSbO4A photocatalyst. The application provides a contain oxygen defect BiSbO4The preparation method of the photocatalyst is simple and effective, and the prepared BiSbO4The photocatalyst has high activity and stability, is not easy to inactivate, has excellent photocatalytic performance on VOCs, and has wide application prospect.
Description
Technical Field
The application relates to the technical field of photocatalysts, in particular to a BiSbO with oxygen-containing defects4A preparation method of the photocatalyst and application thereof.
Background
VOCs (volatile organic compounds) refer to organic compounds having a saturated vapor pressure at ambient temperature of greater than 70Pa and a boiling point at ambient pressure of 260 ℃ or less, or all organic compounds having a corresponding volatility at a vapor pressure of greater than or equal to 10Pa at 20 ℃. The common VOCs mainly comprise benzene, dimethylbenzene, formaldehyde, toluene, styrene, trichloroethylene, trichloromethane, trichloroethane and diisocyanate(TDI), diisocyanatophenyl ester, and the like. Since VOCs are harmful to the human body or the environment, it is necessary to convert VOCs into harmless substances to be discharged. Researches show that the light-driven photocatalysis method can ensure that VOCs can generate oxidation reaction under the action of photocatalyst to generate CO2、H2O and other harmless substances, thereby purifying the environment.
Currently, p-orbital metal oxides are of wide interest as semiconductor photocatalysts in the field of photocatalysis due to their unique electronic structure, e.g., M2Sb2O7(M＝Ca，Sr)，MIn2O4(M＝Ca，Sr，Ba)，MSb2O6(Ca， Zn)，CaBi2O4，ZnBi12O20And BiSbO4. Among these photocatalysts, BiSbO4Attracts attention because of the excellent photocatalytic activity exhibited in the degradation of VOCs. BiSbO4The common preparation method of the photocatalyst is to adopt bismuth nitrate to react with antimony oxide, and the BiSbO prepared by the method4The visible light response range is narrow, and when the photocatalyst is applied to the field of photocatalysis, the activity is low, the deactivation is easy, namely, the VOCs degradation efficiency is low. Therefore, the development of a highly active and non-deactivating BiSbO preparation is urgently needed4A method of photocatalyst.
Disclosure of Invention
The application provides a contain oxygen defect BiSbO4Preparation method and application of photocatalyst for improving BiSbO4Catalytic activity and stability of the photocatalyst.
In a first aspect, the embodiments of the present application provide a BiSbO with oxygen defects4A method for preparing a photocatalyst, the method comprising:
mixing bismuth nitrate pentahydrate and antimony trioxide according to a molar ratio (1.5-2) to 1, and adding 10ml of deionized water to magnetically stir at normal temperature;
dropwise adding a sodium hydroxide solution into the stirred solution, and adjusting the pH value to 1;
carrying out high-temperature hydrothermal reaction on the solution with the pH adjusted, and cooling to obtain a mixed system;
taking the precipitate of the mixed system, and centrifugally washing the precipitateDrying the precipitate to obtain pure phase BiSbO4；
Pure phase BiSbO4Placing under an ultraviolet lamp, and carrying out ultraviolet lamp illumination reaction for 55-60min to obtain the oxygen-containing defect BiSbO4。
Optionally, the molar ratio of the bismuth nitrate pentahydrate to the antimony trioxide is 2: 1.
optionally, the concentration of the sodium hydroxide solution is 1-1.5 mol/L.
Optionally, the temperature of the high-temperature hydrothermal reaction is 120-200 ℃, and the reaction time is 48 h.
Optionally, the solution used for the centrifugal washing is ethanol and deionized water, and the centrifugal washing comprises: washing with deionized water and ethanol successively, and repeating the washing for three times.
Optionally, the ultraviolet lamp is a mercury lamp, and the power of the ultraviolet lamp is 300W.
In a second aspect, the present application provides, in part, a BiSbO with oxygen defects prepared by the method of any one of the first aspects4The application of the photocatalyst in removing formaldehyde or toluene through photocatalysis.
The invention provides a BiSbO with oxygen-containing defects4Preparation method and application of photocatalyst, and oxygen-containing defect BiSbO prepared by the method4The photocatalyst may be BiSbO due to the formation of oxygen defects4A defect intermediate energy level is constructed between a valence band and a conduction band of the photocatalyst, the transition excitation path of photo-generated electrons from the valence band to the conduction band is changed, the transfer conversion of photo-generated charges is promoted, the recombination of photo-generated electron-hole pairs is further inhibited, and finally the prepared oxygen-containing defect BiSbO is formed4The removal rate of VOCs by the photocatalyst is improved. BiSbO with oxygen-containing defects prepared by the preparation method4The photocatalyst has high catalytic activity and stability, is not easy to inactivate, has a simple preparation method, has excellent photocatalytic performance on VOCs, and has a wide application prospect.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a BiSbO containing oxygen defect provided by the application4A flow diagram of a photocatalyst preparation method;
FIG. 2 is an XRD pattern of the products obtained in examples 1 to 4 and comparative example 1, (XRD is an abbreviation for X-ray diffraction, namely X-ray diffraction);
FIG. 3(A) is a high-resolution XPS map (the XPS map is an abbreviation for X-ray photoelectron spectroscopy), for Bi4f, of each of the products obtained in example 4 and comparative example 1;
FIG. 3(B) is a high resolution XPS plot of Sb3d for the products from example 4 and comparative example 1, respectively;
FIG. 4 is a solid phase EPR chart of the products obtained in example 4 and comparative example 1 (ERR chart is an abbreviation for Electron Paramagnetic Resonance);
FIG. 5 is an SEM image of the products obtained in example 4 and comparative example 1 (SEM is an abbreviation for scanning electron microscope, namely, scanning electron microscope);
FIG. 6 is an HRTEM image of the products obtained in example 4 and comparative example 1 (HRTEM is an abbreviation for high resolution transmission electron microscope, i.e., high resolution transmission electron microscope);
FIG. 7 is a PL diagram of the products obtained in example 4 and comparative example 1, (PL is an abbreviation for Photolutenescence, i.e., a fluorescence spectrum);
FIG. 8 is a graph of UV-Vis DRS of the products obtained in example 4 and comparative example 1 (UV-Vis DRS is UV-Visible dispersion-reflection spectrum, i.e. diffuse reflection in the UV-Visible);
FIG. 9(A) is a graph showing the degradation efficiency of the products obtained in examples 2 to 4 to formaldehyde degradation under UV light;
FIG. 9(B) is an in situ infrared diagram of formaldehyde for the product obtained in example 4;
FIG. 10(A) is a graph showing the degradation efficiency of the products obtained in examples 2 to 4 and p25 photocatalyst for the degradation of toluene under UV light;
FIG. 10(B) is a toluene in situ infrared image of the product obtained in example 4;
FIG. 11 shows the product obtained in example 4 and p25 photocatalyst under UV conditions with superoxide anion (. O)2-) is detected;
FIG. 12 is a graph showing the detection of hydroxyl radical (. OH) under UV light of the product obtained in example 4 and a p25 photocatalyst.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, the present application is described in further detail with reference to the accompanying drawings and the detailed description.
The embodiment of the application discloses oxygen defect BiSbO4Preparation method and application of photocatalyst for improving BiSbO4Catalytic activity and stability of the photocatalyst.
As shown in FIG. 1, the application provides a BiSbO containing oxygen defect4A method for preparing a photocatalyst, the method comprising the steps of:
s101, mixing bismuth nitrate pentahydrate and antimony trioxide according to a molar ratio (1.5-2):1, and adding 10ml of deionized water to magnetically stir at normal temperature.
Optionally, the bismuth nitrate pentahydrate (Bi (NO)3)3·5H2O) and antimony trioxide (Sb)2O3) Mixing according to a molar ratio of (1.5-2) to 1, preferably 2:1, that is, the molar ratio of Bi to Sb in the starting material should be 1:1, since BiSbO4The molar ratio of Bi to Sb in the photocatalyst is 1:1, so the molar ratio of Bi to Sb in the starting material should be 1:1, for example, 5.0mmol of Bi (NO) is selected3)3·5H2O：2.5mmol Sb2O3The molar ratio of Bi to Sb is 1: 1. An excessively large proportion of Bi increases the content of Bi, and an excessively small proportion of Sb decreases the content of Sb, both of which affect BiSbO4And (4) generating.
In the step, the bismuth nitrate pentahydrate and the antimony trioxide are put into a container (such as a beaker) according to the molar ratio of 2:1 to be mixed, then a proper amount of deionized water is added, magnetons are added, and the mixture is placed on a stirrer at the temperature and stirred for dissolution.
S102, a sodium hydroxide solution was added dropwise to the stirred solution, and the pH was adjusted to 1.
Optionally, the concentration of the sodium hydroxide solution is 1-1.5 mol/L. Preferably 1 mol/L.
In this step, a sodium hydroxide solution was added dropwise to the solution stirred uniformly in step S101, and the pH was adjusted to 1, thereby obtaining a white turbid solution. The pH was adjusted to 1 in order to obtain a highly crystalline and intact BiSbO4The BiSbO can not be obtained by the photocatalyst when the PH is too large or too small4Structures other than some Bi, Sb6O13、Sb2O3、Bi2O3And the like.
And S103, carrying out high-temperature hydrothermal reaction on the solution with the pH adjusted, and cooling to obtain a mixed system.
Optionally, the temperature of the high-temperature hydrothermal reaction is 120-200 ℃, and the reaction time is 48 h.
In the step, the white turbid solution obtained after the pH is adjusted in the step S103 is subjected to high-temperature hydrothermal reaction, and is cooled to room temperature after the hydrothermal reaction is finished, and then the solution is taken out to obtain the BiSbO-containing solution4The mixed system of (1).
If the temperature of the high-temperature hydrothermal reaction is lower than 120 ℃, BiSbO cannot be generated4Structure; the hydrothermal temperature is kept within 200 ℃ as much as possible, and the hydrothermal temperature exceeding 200 ℃ has certain danger; the reason for choosing a reaction time of 48h is: insufficient time will be for BiSbO4The morphology of (a) has an influence, thereby affecting the activity.
S104, taking the precipitate of the mixed system, centrifugally washing the precipitate, and drying to obtain pure-phase BiSbO4。
Optionally, the solution used for the centrifugal washing is ethanol and deionized water, and the centrifugal washing comprises: washing with deionized water and ethanol successively, and repeating the washing for three times.
The sample is dried at 60 ℃ which is a common temperature, so that the sample can be dried quickly and the influence on the catalyst is small.
In this step, after the high-temperature hydrothermal reaction in step S103, the solid-liquid mixture obtained by cooling to room temperature is centrifugally washedWashing, namely firstly washing the impurities in the BiSbO solution with deionized water, then washing with ethanol for bringing the water away so as to facilitate easy drying, then repeatedly washing for three times, taking out the product and drying to obtain the pure-phase BiSbO4。
S105, mixing the pure phase BiSbO4Placing under an ultraviolet lamp, and carrying out ultraviolet lamp illumination reaction for 50-60min to obtain the oxygen-containing defect BiSbO4。
Optionally, the ultraviolet lamp is a mercury lamp, and the power of the ultraviolet lamp is 300W.
In this step, pure phase BiSbO4Under the irradiation of ultraviolet light, BiSbO4Valence band electrons are excited to a conduction band, the electrons and holes migrate to the surface, the holes react with oxygen ions on the surface to form oxygen vacancies, namely oxygen-containing defects, and the oxygen-containing defects BiSbO are obtained4A photocatalyst.
The time of the ultraviolet irradiation is controlled to be 50-60min, preferably 55min, so that the defect concentration can be kept in a stable state.
According to the technical scheme, the embodiment of the application provides the oxygen-containing defect BiSbO4A method of preparing a photocatalyst, the method comprising: adding bismuth nitrate pentahydrate and antimony trioxide into a beaker, adding water, and magnetically stirring at room temperature until the bismuth nitrate pentahydrate and the antimony trioxide are dissolved; then, dropwise adding a sodium hydroxide solution to adjust the pH value to 1 to obtain a white turbid solution; carrying out high-temperature hydrothermal reaction on the white turbid solution, cooling to room temperature after the hydrothermal reaction is finished, and taking out the white turbid solution; the obtained precipitate is centrifugally washed by water and absolute ethyl alcohol and dried to obtain pure-phase BiSbO4(ii) a The pure phase BiSbO obtained in the above way4Is recycled after being used for a 300W mercury lamp illumination test to obtain the BiSbO with oxygen-containing defects4. BiSbO with oxygen-containing defects shown in the embodiment of the application4The photocatalyst has high catalytic activity and stability and the preparation method is simple.
Furthermore, through the construction of oxygen defects, a plurality of defect intermediate energy levels are formed between the valence band and the conduction band of the photocatalyst, the excitation transmission path of photoproduction electrons is changed, the transfer and conversion of photoproduction charges are promoted, and the recombination of photoproduction electron-hole pairs is further inhibitedAnd (6) mixing. In addition, the oxygen-containing defect BiSbO prepared by the preparation method shown in the embodiment of the application4The catalyst has low production cost.
The present application is further illustrated by the following specific examples.
TABLE reaction conditions for the various examples
For the sake of convenience of description, the product obtained in comparative example 1 is designated as BiSbO in the drawing4200-fresh, the product obtained in example 1 being designated BiSbO4120-product from example 2 as BiSbO 4160, the product obtained in example 3 is designated BiSbO4180, the product obtained in example 4 is designated BiSbO4-200-used。
To verify the oxygen-containing defect BiSbO prepared in the above example4The characteristics of the photocatalyst, namely BiSbO with oxygen-containing defects in multiple characterization modes4Photocatalyst and pure phase BiSbO4The characterization comparison of the photocatalyst is carried out, and the characterization results are analyzed and explained below.
Characterization experiment 1:
to verify the structure of the products obtained in examples 1 to 4 and comparative example 1, XRD analysis was performed on each product, the XRD pattern is shown in FIG. 2, and it can be seen in FIG. 2 that the peaks of the products obtained in comparative example 1 and example 4 are substantially identical, indicating that BiSbO, an oxygen defect, is obtained after UV illumination4The photocatalyst is still BiSbO4The photocatalyst does not show the existence of Bi simple substance, and the crystal phase structure is not changed. In each of examples 1, 2 and 3, a small amount of hetero-peaks were observed as compared with comparative example 1, indicating that the crystallinity was the best when the hydrothermal reaction temperature was controlled at 200 ℃, i.e., the crystal structure was the best in example 4.
Characterization experiment 2:
in order to examine the oxygen-containing defect BiSbO prepared in example 4 of the present application4The photocatalyst was shifted in energy level, and the products of comparative example 1 and example 4 were subjected to high-resolution XPS charts for Bi4f, respectively, as shown in FIG. 3(A), whereby it was found that the oxygen-containing defective BiSbO prepared in example 4 was4Photocatalyst in comparison with pure phase BiSbO prepared in comparative example 14The photocatalyst tends to move slightly to a low level.
Characterization experiment 3:
in order to further examine the oxygen-containing defects BiSbO of the present application4The photocatalyst was shifted in energy level, and the products of comparative example 1 and example 4 were subjected to respective high-resolution XPS charts of Sb3d, as shown in FIG. 3(B), whereby it was found that the oxygen-containing defective BiSbO prepared in example 4 was4Photocatalyst in comparison with pure phase BiSbO prepared in comparative example 14The photocatalyst tends to move slightly to a low level.
Characterization experiment 4:
in order to detect defects in example 4, the products obtained in comparative example 1 and example 4 were subjected to defect testing by EPR analysis, the EPR profile is shown in FIG. 4, and in FIG. 4, an oxygen defect EPR signal appears at the position of g-1.956, which directly confirms that the product obtained in example 4 contains oxygen defect BiSbO4Presence of oxygen defects of the photocatalyst.
Characterization experiment 5:
for examining the oxygen-containing defect BiSbO prepared in example 4 of the present application4Morphology of the photocatalyst, SEM analysis of the products obtained in comparative example 1 and example 4, as shown in FIG. 5, it can be seen that pure phase BiSbO prepared in comparative example 14Photocatalyst and oxygen-containing defective BiSbO prepared in example 44The photocatalysts have walnut-shaped appearance, which shows that the illuminated BiSbO4BiSbO with the appearance not changed before and after illumination, the surface of the product prepared in example 4 is rougher, and the oxygen-containing defects4The photocatalyst has a porous structure.
Characterization experiment 6:
pure phase BiSbO prepared by comparative example 14Photocatalyst and oxygen-containing defective BiSbO prepared in example 44HRTEM analysis of the photocatalyst revealed that clear lattice fringes were observed in FIG. 6, as shown in FIG. 6, confirming that the phase-pure BiSbO prepared in example 14Photocatalyst and oxygen-containing defect BiSbO4The photocatalysis is that the {112} crystal face is exposed.
Characterization experiment 7:
for testing oxygen defect pair BiSbO4Effect of photogenerated carriers on the pure phase BiSbO prepared in comparative example 14Photocatalyst and oxygen-containing defective BiSbO prepared in example 44PL analysis of the photocatalyst showed a fluorescence spectrum as shown in FIG. 7, and in FIG. 7, it can be seen that the fluorescence intensity of the product obtained in example 4 was reduced compared to that of the product obtained in comparative example 1, demonstrating that the oxygen-deficient BiSbO obtained in example 4 was obtained4The photocatalyst promotes the separation of the photo-generated electrons and holes, that is, the oxygen-containing defect BiSbO4The photocatalyst can effectively inhibit the recombination of photo-generated electrons and holes and improve the separation efficiency of photo-generated carriers.
Characterization experiment 8:
to inspect oxygen-containing defects BiSbO4Effect of the light absorption Range of the photocatalyst on the pure-phase BiSbO obtained in comparative example 14Photocatalyst and oxygen-containing defective BiSbO obtained in example 44The ultraviolet-visible diffuse reflection test of the photocatalyst is carried out, the ultraviolet-visible diffuse reflection spectrum result is shown in figure 8, and the product obtained in the example 4 has the advantages that the absorption capacity of the product to light in the ultraviolet-visible-infrared region is increased and the red shift phenomenon occurs compared with the product obtained in the comparative example 1, which indicates that the oxygen-containing defect BiSbO is generated4The photocatalyst widens the light absorption range and improves the light absorption capacity.
To test the oxygen-containing defective BiSbO prepared in examples 2 to 44The photocatalytic activity of photocatalyst, this application provides photocatalysis performance detection experiment, has done the degradation experiment respectively to formaldehyde and toluene, and specific experimentation is as follows:
(1) formaldehyde photocatalytic degradation experiment:
0.4 g of each of the oxygen-containing defective BiSbO prepared in examples 2 to 44The photocatalyst is placed in a formaldehyde continuous flow reactor.
Under the dark condition, when the concentration of formaldehyde is balanced, a mercury lamp with the power of 300W is used as an ultraviolet light source, and the light is turned on to irradiate the photocatalyst; wherein, the formaldehyde degradation test process conditions are as follows: wet air 0.5L/min, dry air 0.3L/min, formaldehyde gas flow 0.02L/min.
As shown in FIG. 9(A), which is a graph showing the formaldehyde degradation efficiency, it can be seen that the oxygen-containing defective BiSbO prepared in example 44The degradation rate of the photocatalyst to formaldehyde is the highest and is about 89.1%, and the degradation rate gradually becomes stable along with the prolonging of time. Wherein the degradation rate is calculated by the formula of eta (%) ═ 1-C/C0)×100％，C0The initial formaldehyde concentration and C is the instantaneous concentration of formaldehyde after 1h of illumination.
FIG. 9(B) is BiSbO with oxygen-containing defects prepared in example 44The photocatalyst degrades formaldehyde (HCHO) in situ infrared graph under different ultraviolet illumination time, and the curves from bottom to top in the graph are as follows: background, adsorption balance, illumination for 2min, illumination for 4min, illumination for 8min, illumination for 16min, illumination for 24min, illumination for 32min and light-off for 10min, and BiSbO is generated along with the increase of the time of ultraviolet illumination4Gradually changed from white at first to gray and finally to black (due to picture color limitation, not shown in the figure), and BiSbO with oxygen defect4The degradation effect of the photocatalyst on formaldehyde gradually becomes stable along with the deepening of the color, which shows that the activity is still maintained in a stable state due to the generation of dynamic defects under the irradiation of ultraviolet light. The method provided by the application is low in economic cost and simple and easy to operate.
(2) Toluene photocatalytic activity experiment:
0.4 g of each of the oxygen-containing defective BiSbO prepared in examples 2 to 44The photocatalyst and p25 (titanium dioxide) were placed in a toluene continuous flow reactor.
Under the dark condition, when the concentration of toluene reaches the balance, a mercury lamp with the power of 300W is used as an ultraviolet light source, and the light is turned on to irradiate the photocatalyst; wherein the toluene degradation test process conditions are as follows: wet air 0.5L/min, dry air 0.44L/min, toluene flow 0.06L/min.
As shown in FIG. 10(A), which is a graph showing the efficiency of toluene degradation, it can be seen that example4 oxygen-containing defect BiSbO prepared4The photocatalyst has the highest degradation rate of toluene, about 69 percent, and oxygen-containing defect BiSbO is generated along with the prolonging of time4The degradation rate of the photocatalyst to toluene gradually tends to be stable, while the degradation rate of p25 to toluene is unstable after first decreasing and then increasing. Wherein the degradation rate is calculated by the formula of eta (%) ═ 1-C/C0)×100％，C0As the initial toluene concentration, C is the instantaneous concentration of toluene after 1h of light irradiation.
FIG. 10(B) shows the oxygen-containing defective BiSbO prepared in example 44The photocatalyst degrades Toluene (Toluene) in-situ infrared images under different ultraviolet illumination time, and the curves from bottom to top in the images are as follows: background, adsorption balance, illumination for 2min, illumination for 4min, illumination for 6min, illumination for 8min, illumination for 12min, illumination for 16min, illumination for 20min, illumination for 24min, illumination for 28min and light-off for 10min, and BiSbO is generated as the time of ultraviolet illumination increases4The initial white color gradually changes into gray color, and finally becomes black color (due to picture color limitation, not shown in the figure), the degradation effect of the oxygen-containing defect BiSbO4 photocatalyst on toluene gradually becomes stable along with the deepening of the color, which shows that the activity is still maintained in a stable state due to the generation of dynamic defects under ultraviolet illumination. The method provided by the application is low in economic cost and simple and easy to operate.
In addition, superoxide anion (. O)2-, the hydroxyl radical (. OH) is an oxygen-containing defect BiSbO4The photocatalyst degrades the main degradation free radicals of VOCs under the condition of ultraviolet light, and FIG. 11 is the superoxide anion (. O.) in example 4 and p252-) detection of active free radicals under ultraviolet (light on) and non-light (dark) conditions using DMPO (5, 5-dimethyl-1-pyrroline-N-oxide) to capture superoxide anion (. O)2-) and FIG. 11 shows that BiSbO has an oxygen-containing defect4The intensity of the superoxide anion of the photocatalyst is 1.5 times stronger than that of p25 (titanium dioxide), FIG. 12 is a graph of the hydroxyl radical (. OH) under ultraviolet light (light on) and no light (dark) conditions in examples 4 and p25, the hydroxyl radical (. OH) is captured by DMPO, and FIG. 12 shows that the oxygen-containing defect BiSbO is present4The photocatalyst has a 1.5 times stronger hydroxyl radical strength than p25, and therefore, contains oxygen vacanciesTrapped BiSbO4The degradation efficiency and the photocatalytic activity of the photocatalyst on VOCs are far higher than those of p 25.
It is to be noted that the oxygen-containing defective BiSbO provided in the examples of the present application4The catalytic mechanism of the photocatalyst for benzene ring, aldehydes and other air pollutants is the same as that of benzene ring and aldehydes, so that the photocatalyst is representative to degradation tests of formaldehyde and toluene in the embodiment of the application, and the oxygen-containing defect BiSbO provided by the embodiment of the application is oxygen-containing4The photocatalytic degradation principle for other substances is the same as that of formaldehyde/toluene.
Oxygen-containing defect BiSbO prepared by the embodiment of the application4The photocatalyst has high catalytic activity, high degradation efficiency on VOCs, stable catalyst, difficult inactivation and simple and easy degradation operation on VOCs.
The present application has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to limit the application. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the presently disclosed embodiments and implementations thereof without departing from the spirit and scope of the present disclosure, and these fall within the scope of the present disclosure. The protection scope of this application is subject to the appended claims.
Claims (7)
1. Oxygen-containing defect BiSbO4A method for preparing a photocatalyst, the method comprising:
mixing bismuth nitrate pentahydrate and antimony trioxide according to a molar ratio (1.5-2) to 1, and adding 10ml of deionized water to magnetically stir at normal temperature;
dropwise adding a sodium hydroxide solution into the stirred solution, and adjusting the pH value to 1;
carrying out high-temperature hydrothermal reaction on the solution with the pH value adjusted, and cooling to obtain a mixed system, wherein the temperature of the high-temperature hydrothermal reaction is 120-200 ℃;
taking the precipitate of the mixed system, centrifugally washing the precipitate, and drying to obtain pure-phase BiSbO4；
Pure phase BiSbO4Put under an ultraviolet lamp forPerforming ultraviolet lamp illumination reaction for 50-60min to obtain oxygen-containing defect BiSbO4。
2. The method according to claim 1, wherein the molar ratio of bismuth nitrate pentahydrate to antimony trioxide is 2: 1.
3. the method according to claim 1, wherein the concentration of the sodium hydroxide solution is 1 to 1.5 mol/L.
4. The preparation method according to claim 1, wherein the reaction time of the high-temperature hydrothermal reaction is 48 hours.
5. The preparation method according to claim 1, wherein the solvents used for the centrifugal washing are ethanol and deionized water, and the centrifugal washing comprises: washing with deionized water and ethanol successively, and repeating the washing for three times.
6. The method according to claim 1, wherein the ultraviolet lamp is a mercury lamp, and the power of the ultraviolet lamp is 300W.
7. BiSbO with oxygen defects prepared by the preparation method according to any one of claims 1 to 64The application of the photocatalyst in removing formaldehyde or toluene through photocatalysis.
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